铑催化的环丙基取代丙炔酸酯的羰基化反应：串联的 1,3-酰氧基迁移[5+1]环加成反应。
Rhodium-catalyzed carbonylation of cyclopropyl substituted propargyl esters: a tandem 1,3-acyloxy migration [5 + 1] cycloaddition.
机构信息
School of Pharmacy, University of Wisconsin, Madison, Wisconsin 53705, USA.
出版信息
J Org Chem. 2012 Aug 3;77(15):6463-72. doi: 10.1021/jo300973r. Epub 2012 Jul 25.
Abstract
We have developed two different types of tandem reactions for the synthesis of highly functionalized cyclohexenones from cyclopropyl substituted propargyl esters. Both reactions were initiated by rhodium-catalyzed Saucy-Marbet 1,3-acyloxy migration. The resulting cyclopropyl substituted allenes derived from acyloxy migration then underwent [5 + 1] cycloaddition with CO. The acyloxy group not only eased the access to allene intermediates but also provided a handle for further selective functionalizations.
摘要
我们开发了两种不同类型的串联反应，用于从环丙基取代的丙炔酸酯合成高官能化的环己烯酮。这两种反应都是由铑催化的 Saucy-Marbet 1,3-酰氧基迁移引发的。随后，酰氧基迁移得到的环丙基取代的丙二烯经历了与 CO 的 [5 + 1] 环加成反应。酰氧基不仅为得到丙二烯中间体提供了便利，而且为进一步的选择性官能化提供了一个手段。
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本文引用的文献
1
Constructing Tricyclic Compounds Containing a Seven-Membered Ring by Ruthenium-Catalyzed Intramolecular [5+2] Cycloaddition.
Angew Chem Int Ed Engl. 2001 Jun 18;40(12):2313-2316. doi: 10.1002/1521-3773(20010618)40:12<2313::AID-ANIE2313>3.0.CO;2-H.
2
Rhodium(I)-Catalyzed Regioselective Ring- Expanding Rearrangement of Allenylcyclopropanes into Methylenecyclopentenes.
Angew Chem Int Ed Engl. 1998 Apr 3;37(6):837-839. doi: 10.1002/(SICI)1521-3773(19980403)37:6<837::AID-ANIE837>3.0.CO;2-R.
3
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Org Lett. 2012 Mar 16;14(6):1584-7. doi: 10.1021/ol300330t. Epub 2012 Mar 2.
4
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